Castner A.T., Su H., Svensson Grape E. et al. · Journal of the American Chemical Society · 2022 · 5910-5920
Open a family to keep every result attached to its sample, method and conditions.
Paraphrased for this database from the authors’ stated interpretations — never quoted verbatim — and kept separate from reported measurements.
Zr(dcphOH-NDI) is assigned as a porous interpenetrated Zr-organic framework with two interpenetrated 12-connected fcu nets and about 11 A maximum pore diameter.
Caveat: Hydroxyl positions have partial occupancy/disorder in the 3DED model.
5912 · Materials/Methods · Figure 2 · Linked to 5 structured results
Changing electrolyte cation and solvent changes average Dapp_e across more than two orders of magnitude, from 3.23e-9 cm2 s-1 for LiClO4/DMF to 1.30e-11 cm2 s-1 for LiClO4/THF.
Caveat: Averages have large standard deviations for some conditions, especially TBAPF6/DMF.
5915-5916 · Chronoamperometry and Cottrell Analysis · Table 3; Figure 6 · Linked to 4 structured results
Li+ in DMF gives the fastest average Dapp_e even though Li+ engages in strong ion pairing, implying charge propagation is not limited solely by ion-pair association equilibrium.
Caveat: Mechanistic interpretation relies on combining macroscopic electrochemistry with DFT model systems.
5918 · Conclusions · Linked to 3 structured results
DFT suggests a specific Li+ bridge between reduced and neutral NDI linkers delocalises spin over two linkers and sets up concerted cation-coupled electron transfer.
Caveat: Based on finite cluster calculations, not direct experimental observation of the transition state.
5917-5918 · Computational Studies/Conclusions · Figure 8 · Linked to 4 structured results
Lower-polarity THF increases cation association with reduced NDI linkers and yields the slowest apparent diffusion coefficients for Li+ and TBA+ electrolytes.
Caveat: KPF6/THF was simulated for comparison but no experimental Dapp_e was reported in the main table.
5916 · Chronoamperometry and Cottrell Analysis · Figure 6 · Linked to 4 structured results
Charge transport in Zr(dcphOH-NDI)@FTO occurs as cation-coupled electron hopping through redox-active NDI linkers, so measured Dapp_e contains contributions from electron hopping and counter-cation diffusion/migration.
Caveat: Dapp_e is apparent and mechanism-dependent, not a pure microscopic self-exchange diffusion coefficient.
5910-5912 · Abstract/Introduction · Figure 1 · Linked to 3 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| dcphOH-NDI linker | not reported as molecular formula; naphthalene diimide dicarboxylate linkernone · N,N'-bis(3-carboxy-4-hydroxyphenyl)-naphthalene diimide derivative (dcphOH-NDI) | 0D · Model SystemHomogeneous redox-active NDI linker used as MOF linker and electrochemical reference compound. | 5912 · Materials/Methods · Figure 2d |
| fully reduced Zr(dcphOH-NDI) MD model | periodic model; formula not reportedZr4+ dummy atom model for zirconium clusters · NDI-based Zr(dcphOH-NDI) linkers reduced to NDI radical anion states | 3D · Model SystemInterpenetrated PIZOF model in periodic DMF or THF solvent boxes, neutralised with Li+, K+, or TBA+ cations. | 13-14 · Molecular Dynamics and Simulation Methods · Figure S10 |
| Zr6O4(OH)4(OAc)10(NDI-OH)2 DFT cluster model | Zr6O4(OH)4(OAc)10(NDI-OH)2 model systemone Zr6O4(OH)4 cluster capped with acetate ions · two NDI-OH linkers; Li+, K+, or TBA+ counterion variants | 0D · Model SystemSingle cluster with two linkers used for DFT spin-density and cation-bridge calculations. | 18 · DFT setup for single cluster with two linkers · Figure 8 |
| Zr(dcphOH-NDI) | C672N48O272Zr24 (3DED empirical formula)hexanuclear zirconium Zr6O4(OH)4 secondary building units · redox-active naphthalene diimide dcphOH-NDI linkers | 3D · PristinePorous interpenetrated Zr-organic framework (PIZOF), two interpenetrated frameworks with a 12-connected fcu net; maximum pore diameter about 11 A. | 5912 · Materials/Methods · Figure 2 |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| dcphOH-NDI homogeneous linker solutionresearch_0453__mat__mat_dcphoh_ndi_linker | Unknown · Model System · Model | 1 mM in DMF unless otherwise noted; lower than 1 mM in THF and EtOH because of low solubility; 0.5 M supporting electrolyte.glassy carbon working electrode for CV · not applicable | 5914 · Figure 3 caption · Figure 3 |
| reduced Zr(dcphOH-NDI) periodic MD model with Li+, K+, or TBA+research_0453__mat__mat_reduced_zr_dcphoh_ndi_md_model | Model · Model System · Model | All linkers reduced to NDI radical anion state and neutralised by cations in periodic MD.periodic DMF or THF solvent box · not applicable | 5916 · Computational Studies · Figure S10 |
| Li+, K+, and TBA+ two-linker DFT cluster modelsresearch_0453__mat__mat_zr6_two_linker_dft_model | Model · Model System · Model | One alkali ion placed between two NDI oxygen atoms or TBA+ placed near one reduced linker; optimised by DFT.implicit DMF solvation for spin density calculations · not applicable | 5917 · Computational Studies · Figure 8 |
| bulk Zr(dcphOH-NDI) crystals for 3DEDresearch_0453__mat__mat_zr_dcphoh_ndi_pizof | Single Crystal · Target Sample · Pristine Framework | Solvothermally prepared bulk crystals dispersed in ethanol, gently mortared and drop-cast for 3DED.copper TEM grid with holey carbon film for 3DED sample preparation · micrometer-sized crystals; no thickness reported | 12 · Three-dimensional electron diffraction measurements · Figure S8 |
| Zr(dcphOH-NDI)@FTO thin-film electrodesresearch_0453__mat__mat_zr_dcphoh_ndi_pizof | Electrode · Target Sample · Pristine Framework | Solvothermally grown thin films; kept solvent-swelled, non-evacuated before voltammetry; conditioned by 50 CV scans before chronoamperometry.fluorine-doped tin oxide (FTO) · individual films 0.605-1.941 um by cross-section SEM/ImageJ in SI Tables S1-S6 | 5912 · Materials/Methods · Figure S1 |